Mafic phenocrysts from selected products of the last 4 ka volcanic activity at Mt. Vesuvius were investigated for their chemical and O-isotope composition, as a proxy for primary magmas feeding the system. 18O/16O ratios of studied Mg-rich olivines suggest that near-primary shoshonitic to tephritic melts experienced a flux of sedimentary carbonate-derived CO2, representing the early process of magma contamination in the roots of the volcanic structure. Bulk carbonate assimilation (physical digestion) mainly occurred in the shallow crust, strongly influencing magma chamber evolution. On a petrological and geochemical basis the effects of bulk sedimentary carbonate digestion on the chemical composition of the near-primary melts are resolved from those of carbonate-released CO2 fluxed into magma. An important outcome of this process lies in the effect of external CO2 in changing the overall volatile solubility of the magma, enhancing the ability of Vesuvius mafic magmas to rapidly rise and explosively erupt at the surface.